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WO1999026955A1 - Produits d'addition d'antimoine/base de lewis utiles pour l'implantation d'ions sb et la formation de films d'antimoniure - Google Patents

Produits d'addition d'antimoine/base de lewis utiles pour l'implantation d'ions sb et la formation de films d'antimoniure Download PDF

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WO1999026955A1
WO1999026955A1 PCT/US1998/024568 US9824568W WO9926955A1 WO 1999026955 A1 WO1999026955 A1 WO 1999026955A1 US 9824568 W US9824568 W US 9824568W WO 9926955 A1 WO9926955 A1 WO 9926955A1
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Prior art keywords
antimony
lewis base
cio
formula
adduct
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PCT/US1998/024568
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English (en)
Inventor
Michael A. Todd
Thomas H. Baum
Gautam Bhandari
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Advanced Technology Materials, Inc.
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Priority to AU21975/99A priority Critical patent/AU2197599A/en
Publication of WO1999026955A1 publication Critical patent/WO1999026955A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/90—Antimony compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/20—Doping by irradiation with electromagnetic waves or by particle radiation
    • C30B31/22—Doping by irradiation with electromagnetic waves or by particle radiation by ion-implantation

Definitions

  • This invention relates to antimony Lewis base adducts useful as source reagents for applications including Sb-ion implantation and formation of antimonide films.
  • alkyl or aryl metal hydrides such as HSbR2 and H2SbR, wherein R is alkyl, are also unstable.
  • CVD chemical vapor deposition
  • Sb-based heterostructures that display important optoelectronic and electronic properties, including InSb3, InGaSb4, InAsSb5, GaAlSb ⁇ and InSbBiy.
  • Volatile and thermally stable Sb precursors would facilitate the chemical vapor deposition of antimonide thin-films, as required for the large scale, controlled production of antimonide based lasers, detectors and microelectronic sensors.
  • Antimonide materials are attractive for commercial infrared optoelectronic applications.
  • the compositional variety and stoichiometry of IH-V compound semiconductors allows for nearly complete coverage of the infrared spectrum.
  • Bandgaps ranging from 2.5 eV in AlP to 0.2 eV in InSb can be achieved by forming strained thin-films with the proper elemental and stoichiometric compositions.
  • Materials of greatest interest include InSbBi and InAs- SbBig for long wavelength (8-12 mm) infrared detectors, InAsSbo and InGaSbio f° r mid- infrared absorbers in military applications, and InSb/In ⁇ . ⁇ Al ⁇ Sb ⁇ ⁇ light emitting diodes (LEDs) for mid-infrared chemical sensor applications.
  • LEDs light emitting diodes
  • a type- II quantum well superlattice laser comprised of InAsSb active layer with alternating InPSb and AlAsSb cladding layers, provides 3.5 mm emission upon electron injection.
  • mid-infrared lasers comprised of InAs/InGaSb/InAs active regions with lattice-matching to AlSb cladding layers were also demonstrated.
  • the device fabrication requires thin-film processing of elemental aluminum, antimony, gallium and indium to produce both the active and cladding layers, and thereby, presents a significant technological challenge.
  • dopants that can be utilized in very shallow p/n layers. This implies that traditional dopants such as boron (p-type) and phosphorus (n-type) will have to be replaced due to their high mobility in silicon (which results in a breakdown of the junction, even with reduced thermal budgets).
  • p- and n-type dopants are indium and antimony, respectively, due to their greater size and mass, which provide superior diffusion characteristics relative to traditional implant species. These properties make it is possible to use lower implant energies and more advantageous geometries when depositing the shallow p/n junctions that are critical to DRAM storage density increases.
  • suitable volatile antimony and indium precursors are currently unavailable.
  • the present invention relates to antimony/Lewis base adducts having utility, inter alia, as source reagents for ion implantation of antimony and for formation of antimony or antimony-containing films by processes such as chemical vapor deposition, assisted chemical vapor deposition (e.g., laser, light, plasma, ion, etc.), ion implantation, molecular beam epitaxy, and rapid thermal processing.
  • chemical vapor deposition e.g., laser, light, plasma, ion, etc.
  • ion implantation e.g., molecular beam epitaxy
  • rapid thermal processing e.g., rapid thermal processing.
  • Such antimony/Lewis base adducts may have the formula:
  • each R is independently selected from Ci - Cs alkyl, Ci - C ⁇ perfluoroalkyl, Ci - Cs haloalkyl, C6 - Cio aryl. C6 - Cio perfluoroaryl, C6 - Cio haloaryl, C6 - Cio cycloalkyl, substituted C6 - Cio aryl m & na -°; and
  • L is a Lewis base ligand coordinating with SbR3.
  • L may comprise any suitable Lewis base ligand which is compatible and complexes with SbR3.
  • Potentially useful Lewis base species in the broad practice of the present invention include, but are not limited to,
  • G is -O-, -S-, or -NR-, wherein R is H or hydrocarbyl, e.g., Ci - Cg alkyl;
  • R H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl;
  • R H, F, or a sterically acceptable hydrocarbyl substituent;
  • each R , R , and R may be the same as or different from the
  • ligand L examples include tetraglyme, tetrahydrofuran, bipydridine, ammonia, pyridine, 3-phenylpyridine, 3-picoline, 18-crown-6 ethers, and amines/polyamines such as pentamethyldiethylenetriamine (PMDETA), diethylenetriamine (DETA), tetraethylenepentaamine (TEPA) and hexamethyltetraethylenepentaamine (HMTEPA).
  • PMDETA pentamethyldiethylenetriamine
  • DETA diethylenetriamine
  • TEPA tetraethylenepentaamine
  • HMTEPA hexamethyltetraethylenepentaamine
  • the present invention relates to tris(trifluoromethyl)stibine adducts of the formula:
  • the invention relates to a method of depositing antimony on a substrate from an antimony-containing precursor therefor, comprising using as a precursor an antimony/Lewis base adduct of the formula:
  • each R is independently selected from Ci - Cs alkyl, Ci - C$ perfluoroalkyl, Ci - Cs haloalkyl, C - Cio aryl, Co - Cio perfluoroaryl, Co - Cio haloaryl, C - Cio cycloalkyl, substituted C - Cio ar y a °d halo; and
  • L is a Lewis base ligand coordinating with SbR3.
  • the antimony may be deposited by a process selected from the group consisting of chemical vapor deposition, assisted chemical vapor deposition (e.g., laser, light, plasma, ion, etc.), ion implantation, molecular beam epitaxy, and rapid thermal processing.
  • chemical vapor deposition e.g., laser, light, plasma, ion, etc.
  • ion implantation e.g., molecular beam epitaxy
  • molecular beam epitaxy e.g., molecular beam epitaxy, and rapid thermal processing.
  • Still another aspect of the invention relates to a storage and dispensing system for an antimony source reagent, comprising:
  • antimony source reagent comprises an antimony/Lewis base adduct of the formula:
  • each R is independently selected from Ci - Cg alkyl, Ci - C% perfluoroalkyl, Ci - Cs haloalkyl, C ⁇ - Cio aryl, C6 - Cio perfluoroaryl, C - Cio haloaryl, C6 - Cio cycloalkyl, substituted C6 - Cio ar yl and halo; and
  • L is a Lewis base ligand coordinating with SbR3.
  • the sorbent material may suitably comprise a solid physisorbent material.
  • the sorbent material may comprise a liquid sorbent in which the antimony source reagent is soluble, such as polyethers, glycols, cryptanes and crown ethers.
  • Figure 1 shows a vapor phase IR spectrum of tris(trifluoromethylstibine)ammonia.
  • Figure 2 shows a ⁇ C NMR spectrum of Sb(CF3)3 # NH3 evidencing a pronounced downfield shift of the carbon resonances of approximately 3 ppm from the unbound molecule.
  • Figure 3 shows a vapor phase FTIR spectrum of (CF3)3SbNC ⁇ j H5 Lewis-base adduct, in
  • Figure 4 is a schematic representation of the crystal structure of a 3-phenylpyridine tris- trifluoromethylstibine adduct, showing that the Sb-N bond length is unexpectedly long, indicative of a very weak adduct bond.
  • Figure 5 is a schematic representation of a gas storage and dispensing vessel holding a sorbent medium and an antimony source reagent according to the invention.
  • the present invention is based on the discovery of antimony/Lewis base adducts useful, inter alia, for ion implantation and thin film antimonide deposition.
  • the adducts of the invention are markedly less reactive towards oxygen than the parent antimony compounds, yet still retain useful volatility. This combination of properties makes the adducts of the present invention excellent source reagents for ion implant and chemical vapor deposition applications, because they are much safer to use than the parent molecule.
  • the antimony/Lewis base adducts of the invention have the formula:
  • each R is independently selected from Ci - Cs alkyl, Ci - Cs perfluoroalkyl, Cl - Cs haloalkyl, C ⁇ - C o ar yl > Co - Cio perfluoroaryl, C - Cio haloaryl, C6 - Cio cycloalkyl, substituted C6 - Cio ar yl an( l na l°- an£ l
  • L is a Lewis base ligand coordinating with SbR3.
  • L may comprise any suitable Lewis base ligand which is compatible and complexes with SbR3, e.g.,
  • G is -O-, -S-, or -NR-, wherein R is H or hydrocarbyl, e.g., Ci - Cs alkyl;
  • R H, methyl, ethyl, n-propyl, cyanato, perfluoroethyl, perfluoro-n-propyl, or vinyl;
  • R H, F, or a sterically acceptable hydrocarbyl substituent;
  • each R , R , and R may be the same as or different from the
  • the ligand L by way of example may be tetraglyme, tetrahydrofuran, bipydridine, ammonia, pyridine, 3-phenylpyridine, 3-picoline, 18-crown-6 ethers, and amines/polyamines such as pentamethyldiethylenetriamine (PMDETA), diethylenetriamine (DETA), tetraethylenepentaamine (TEPA) or hexamethyltetraethylenepentaamine (HMTEPA).
  • PMDETA pentamethyldiethylenetriamine
  • DETA diethylenetriamine
  • TEPA tetraethylenepentaamine
  • HMTEPA hexamethyltetraethylenepentaamine
  • antimony source reagents of the invention may be employed to deposit antimony on a substrate, e.g., by a process such as chemical vapor deposition, assisted chemical vapor deposition (e.g., laser, light, plasma, ion, etc.), ion implantation, molecular beam epitaxy, or rapid thermal processing.
  • a process such as chemical vapor deposition, assisted chemical vapor deposition (e.g., laser, light, plasma, ion, etc.), ion implantation, molecular beam epitaxy, or rapid thermal processing.
  • antimony source reagents of the invention may be effected by reacting the antimony compound SbR3 with the Lewis base species L to yield the adduct, SbR3 L.
  • the antimony compound SbR3 may in turn be formed from the corresponding halide SbX3 by non-aqueous reaction to form the hydride,
  • the halide SbR3 may be directly reacted with the Lewis base, L, to form the adduct, SbR3 » L, by reactions such as:
  • antimony metal may be employed to prepare the adducts.
  • the liquid source adducts can be utilized for forming antimony or antimony-containing films on substrates by any suitable means and/or method, including for example liquid delivery chemical vapor deposition, wherein the liquid is vaporized and antimony is deposited on a substrate in a CVD reactor from the vapor phase of the vaporized precursor.
  • Solid source reagents can be dissolved or suspended in a compatible solvent medium and likewise be employed in liquid delivery chemical vapor deposition, wherein the solution or suspension is vaporized and antimony is deposited on a substrate in a CVD reactor from the vapor phase of the precursor material.
  • conventional bubbler techniques may be employed.
  • Lewis-base adducts of the invention are adducts of Sb(CF3)3 with ammonia, pyridine and phenylpyridine.
  • Related acid-base adducts may also be synthesized within the broad scope of the invention (e.g., species with a lone-pair of electrons capabale of d ⁇ -p ⁇ backbonding with Sb such as Me2 ⁇ , NMe3, etc.).
  • the tris(trifluoromethylstibine)ammonia adduct is a mobile colorless liquid with a room temperature vapor pressure of approximately 22 Torr suitable for use as a precursor both for ion implantation and for chemical vapor deposition because NH3 is a thermally robust, carbon-free adduct that does not readily crack at low temperature.
  • the thermal stability of such adduct eliminates carbon or nitrogen contamination.
  • the parent molecule, Sb(CF3)3 is known to thermally decompose at approximately 200 C, which is consistent with the ability of the adduct to enable high purity antimonide film growth at low processing temperatures.
  • the adduct precursor molecule contains excellent leaving groups in the form of CF3 radicals that can easily combine with each other to form hexafluoroethane, as a thermally stable low-temperature byproduct. Accordingly, the precursor H3N: Sb(CF3)3 is a good source of pure Sb, with carbon contamination being kept to a minimum in use thereof.
  • H5C5N Sb(CF3)3 and tris(trifluoromethylstibine)-3-phenylpyridine adduct may be usefully employed in CVD and ion-implantation applications.
  • H5C5N Sb(CF3)3 is a stable, white solid that may be conveniently formed by the reaction of anhydrous pyridine with pure Sb(CF3)3.
  • This low-melting, solid adduct (which melts at approximately 40-41 C) has a vapor pressure of nearly 3 Torr at room temperature (25 C) and displays a greatly reduced reactivity towards oxygen relative to the pure compound.
  • the pure compound reacts explosively upon exposure to air, while the adduct merely fumes upon exposure.
  • this species may be usefully employed as a stable low-temperature source of antimony in CVD applications.
  • the vapor phase IR spectrum of the adduct H5C5N: Sb(CF3)3 is shown in Figure 3.
  • the crystal structure of the other adduct, tris(trifluoromethylstibine)-3-phenylpyridine, is shown in Figure 4 and displays a very interesting packing sequence.
  • the length of the Sb-N bond which is exceptionally long. This unexpectedly long bond length indicates that the adduct is only very weakly bound, consistent with low temperature thermal decomposition in use of the adduct, so that the adduct provides a source of pure Sb for low temperature deposition applications, e.g., in chemical vapor deposition.
  • Ion implant applications may suitably involve the provision of a polymer backbone with suitable donor groups that bind Sb(CF3)3 weakly (as shown in the crystal structure).
  • the adducts of the invention have broad use as antimony sources for the CVD of antimonides and in the ion implantation of Sb + in the semiconductor industry, e.g., for the fabrication of UI-V compound semiconductors, and for forming thin-film, long wavelength infrared detecting materials such as InSb, InAsSb, InGaSb, InSbBi and InAsSbBi.
  • the antimony source reagents of the invention may be utilized to form InSb as an advantageous material for high speed devices due to its high electron mobility and maximum electron drift velocity.
  • the adducts of the invention achieve a substantial advance in the art over traditional alkyl-antimony precursors.
  • Such traditional precursors are not useful for the growth of high quality, crystalline InSb epitaxial layers which possess abrupt interfaces, because of the high processing temperatures (> 460°C) required for such traditional source reagents.
  • Adducts of the invention may be employed as precursors for depositing antimony in the fabrication of long wavelength (8-12 mm) infrared detector devices based upon InSbBi and InAsSbBi, as competitors to traditional, but more difficult to process, HgCdTe materials- based devices.
  • Adducts of the invention may be employed as precursors for depositing antimony in the fabrication of other devices, e.g., infrared optoelectronic devices such as Type-II quantum well lasers based on superlattice LED heterostructures (with quantum well structures comprised of materials such as InAsSb with cladding layers of InPSb and AlAsSb) to provide mid-infrared range emissions, chemical sensor systems, infrared military counter- measure devices, mid-infrared lasers involving active regions comprised of InAs/InGaSb InAs with lattice matching to AlSb cladding layers, InSb/In ⁇ -.
  • infrared optoelectronic devices such as Type-II quantum well lasers based on superlattice LED heterostructures (with quantum well structures comprised of materials such as InAsSb with cladding layers of InPSb and AlAsSb) to provide mid-infrared range emissions, chemical sensor systems, infrared
  • the antimony source reagents of the present invention may be provided in a preferred form as a sorbate which is sorptively retained on a suitable sorbent medium in a storage and dispensing vessel holding the physical sorbent and the antimony source reagent material, in accordance with the disclosure of U.S. Patent 5,518,528 issued May 21, 1996 in the names of Glenn M. Tom and James V. McManus.
  • the storage and dispensing vessel is equipped with suitable dispensing means such as a conventional valve head assembly, to provide on- demand dispensing of the storage antimony source gas.
  • suitable dispensing means such as a conventional valve head assembly
  • FIG. 5 is a schematic representation of a gas storage and dispensing vessel 10 holding a sorbent medium 12 and a sorbate antimony adduct according to the invention.
  • the gas storage and dispensing vessel may be constructed and arranged as more fully described in the aforementioned Tom et al. patent, and features a dispensing manifold 14 joined to the valve head 16 of the vessel as illustrated.
  • the antimony adduct source reagents of the present invention may be stored for extended periods of time, and supplied on demand for such applications as ion implantation and chemical vapor deposition.
  • the adducts of the present invention may optionally in some applications be derivatized to the extent of any hydrogen substituent(s) on the antimony nuclear atom, by replacing one or more of such hydrogen substituent(s) with deuterium ( ⁇ lH) or tritium (- ⁇ iH) isotope, as more fully described in our co-filed United States Patent Application No. 08/977,225 filed November 24, 1997 in the names of Michael A. Todd, Thomas H. Baum and Gautam Bhandari for "Stable Hydride Source Compositions for Manufacture of Semiconductor Devices and Structures," the disclosure of which is hereby incorporated herein by reference in its entirety.
  • Such derivatization may be desired for further enhancing the stability of the adducts of the present invention.
  • the invention has been described herein with specific and primary reference to antimony as the metal species of interest in the adducts of the present invention, the invention is not thus limited, and may find application in other metal source compositions, e.g., with metals such as aluminum, gallium, tin, germanium, indium, etc., or other Group in, IV or V metal or a transition metal, in place of antimony.
  • Thin Film Deposition The thin films described in this work were deposited in a horizontal, resistively heated, hot-walled 1.5" CVD reactor. Temperature control was accomplished using a Eurotherm model 847 temperature controller and reactant and carrier gases were introduced via mass flow controllers. Pumping of the reactor system was accomplished using a liquid nitrogen trapped diffusion pump and and resulted in a base pressure approaching 10 " " Torr. Processing pressures were monitored via a baratron capacitance manometer gauge and varied by changing the reactant and carrier gas flow rates. The condensible volatiles of the reactions were collected in a glass trap cooled to liquid nitrogen temperature and were analyzed using FTIR and, when possible, NMR. Analysis of these byproducts in conjunction with analysis of the film properties and compositions allowed for optimization of the processing conditions.
  • Tris(trifluoromethyl)stibine, Sb(CF3)3 was synthesized via reaction in a high-pressure stainless steel autoclave.
  • Lewis base adducts of tris(trifluoromethyl)stibine containing ammonia, pyridine, 3-phenyl- pyridine and 3-picoline were also synthesized and found to be suitable precursors for antimonide CVD.
  • Tris(trifluoromethyl)stibine, Sb(CF3)3, denoted hereafter as compound 1 was prepared at 175°C and 40 atm in a 90 ml stainless steel Parr autoclave by reacting antimony metal with trifluoromethyl iodide. The pure compound was isolated from iodobis(trifluoromethyl)stibine and diiodotrifluoromethylstibine via trap-trap vacuum distillation in 35% yield.
  • Sb(CF3)3 is a colorless, mobile liquid (mp. -58°C) with a room temperature vapor pressure of 81 Torr. It is thermally stable up to 200°C, but reacts explosively on exposure to oxygen, and was handled accordingly. These physical properties greatly limit the utility of compound 1 for CVD applications.
  • the pyridine adduct, compound 2 is a colorless solid (mp. ⁇ 37°C) with a room temperature vapor pressure of approximately 2 Torr while the 3-phenylpyridine adduct, compound 3, is a colorless solid with a room temperature vapor pressure below one Torr.
  • the scanning thermal analysis and thermogravimetric analysis (STA / TGA) data for compound 2 reveal that the adduct melts and sublimes cleanly. These properties, combined with a marked decrease in reactivity towards oxygen exposure, make compound 2 highly useful as a CVD precursor. Crystallographic data was collected from crystals of 2, and showed that its structure of the crystals was highly symmetrical in nature.
  • ammonia and 3-picoline adducts, compounds 4 and 5, respectively, are both mobile colorless liquids at room temperature.
  • Compound 4 displays a room temperature vapor pressure of 31 Torr and is much less reactive towards oxygen than the parent compound (merely fuming on exposure to oxygen, rather than exploding). These properties, coupled with the lack of carbon atoms in the adduct ligand make compound 4 a useful CVD source.
  • N-H stretch at 3033 cm The decrease in the symmetry of the adduct relative to the free molecules is readily observed by the lack of the p and r branches in the ammonia-related stretching and bending modes (3033 and 1374 cm ), which was compared with the spectrum of the small amount of unbound ammonia added to the sample (N-H stretching at 3331 cm ) for reference purposes.
  • Compound 1 was thermally decomposed in a horizontal, hot-walled, low- pressure CVD reactor at temperatures as low as 275°C to yield thin films of antimony. Most depositions, however, were carried out at 350-400°C due to low growth rates below 350°C.
  • the precursor was introduced pure and in diluted mixtures of compound 1 and H2. Typical growth times were thirty minutes to one hour and resulted in thick films of antimony. Films were deposited on Si, Pt/Si, glass (Pyrex) and Si ⁇ 2- Good adherence was observed on Pyrex glass and Pt/Si, but poor adherence was observed on Si and Si ⁇ 2- In addition, thick films deposited on Pt/Si were observed to have pinholes.
  • the decomposition byproducts for many depositions were collected in a liquid nitrogen cold trap and later examined using FTIR spectroscopy.
  • the main components of the volatile byproducts were identified as tetrafluoroethylene, hexafluoroethane and unreacted starting material.
  • a white solid residue was also observed in the reactor tube outside the hot zone.
  • An FTIR analysis of the material revealed that it possessed strong C-F stretches at 1165 - 1050 cm , suggesting that it may have been a mixture of C-F polymers formed by recombination of CF3 and CF2 radicals produced during the decomposition.
  • XRD x-ray diffraction
  • EDS energy dispersive x-ray analysis
  • FTIR Fourier transform infrared spectroscopy
  • the bomb was manually agitated during this process to insure adequate mixing of the reagents. During the course of the reaction the pressure was noted to steadily decrease (indicating the consumption of CF3I and the formation of Sb(CF3)3) until it reached a value of approximately 10 atm.
  • the bomb was allowed to cool and then attached to a high vacuum manifold via stainless steel bellows tubing. The volatile products were then passed through traps held at -25 C, -70 C and -196°C in order to isolate Sb(CF3)3 in the -70°C trap.
  • the -196°C trap was found to contain unreacted CF3I and and a small amount of a mixture of fluorocarbon gases (eg.
  • Tris(trifluormethyl)stibine is a colorless, mobile liquid (mp. -58 C) with a vapor pressure of 81 Torr at room temperature. It reacts explosively on contact with oxygen and was handled with great care.
  • Sb(CF3)3 was characterized using vapor phase FTIR, mass spectrometry (via ion implantation testing) and NMR, as well as by crystal structure determination of the phenylpyridine adduct.
  • Vapor Phase FTIR 2379 cm “1 (vw), 2276 cm “1 (vw), 2219 cm “1 (vw), 2180 cm “1 (w), 1326 cm “1 (vw), 1274 cm “1 (w), 1242 cm “1 (w), 1190 cm' 1 (vs), 1146 cm “1 (vs), 1127 cm “1 (vs), 1092 cm “1 (vs), 1069 cm “1 (sh), 1042 cm “1 (w), 990 cm “1 (vw), 867 cm “1 (vw), 723 cm' 1 (m), 517 cm “1 (vw).
  • H3N:Sb(CF3)3 is a mobile liquid with a room temperature vapor pressure of 31 Torr.
  • the molecule exhibits remarkably reduced reactivity towards air relative to Sb(CF3)3, merely fuming on exposure, rather than igniting.
  • H5C5N:Sb(CF3)3 is a volatile white solid which displays a much higher degree of stability than the parent molecule, Sb(CF3)3, with respect to air reactivity.
  • Vapor Phase FTIR 3692 cm “1 (vw), 3092 cm-1 (w), 3085 cm “1 (w), 3039 cm “1 (w), 2966 cm “1 (vw), 2177 cm “1 (vw), 1585 cm “1 (w), 1506 cm “1 (vw), 1447 (w), 1252 cm “1 (w), 1190 cm” 1 (vs), 1148 cm “1 (s), 1128 cm “1 (vs), 1092 cm “1 (vs), 1072 cm “1 (m,sh), 1042 cm “1 (w), 1015 cm “1 (w), 952 cm “1 (vw), 867 cm “1 (vw), 795 cm “1 (w), 734 cm “1 (m), 711 cm ' l (m), 685 cm'l (vw), 607 cm”l (vw), 515 c ⁇ r (w).
  • Sb(CF3)3 - NC5H5(CgH5) is a viscous brownish oil which exhibits a vapor pressure of less than one Ton at room temperature. It is markedly less reactive towards oxygen than Sb(CF 3 ) 3 .
  • Vapor Phase FTIR 2968 cm “1 (w), 2931 cm “1 (w,sh), 2880 cm “1 (vw), 2461 cm “1 (vw), 1248 cm” 1 (w), 1190 cm “1 (s), 1145 cm “1 (m), 1125 cm “1 (s), 1091 cm “1 (vs), 1039 cm “1 (vw), 721 cm “1 (w).
  • the present invention provides antimony/Lewis base adducts having industrial applicability as source reagents for forming antimonide films and implanting antimony ions.
  • the adducts of the invention therefore may be employed in accordance with the process of the invention, to fabricate advanced semiconductor devices such as lasers, detectors, microelectronic sensors, and other optoelectronic device structures.
  • the adducts of the invention make it possible to use lower implant energies and more advantageous geometries when depositing shallow p-n junctions in device structures such as DRAM devices, thereby achieving a substantial advance in the art with respect to storage density of such devices.

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  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un produit d'addition d'antimoine/base de Lewis représenté par la formule SbR3.L, dans laquelle chaque R est sélectionné indépendamment dans le groupe constitué par un alkyle en C1-C8, un perfluoroalkyle en C1-C8, un haloalkyle en C1-C8, un aryle en C6-C10, un perfluoroaryle en C6-C10, un haloaryle en C6-C10, un cycloalkyle en C6-C10, un aryle et un halo substitués en C6-C10; et L est un ligand de base de Lewis se coordonnant avec SbR3. Les produits d'addition de l'invention sont utiles comme compositions de source métallique en vue d'un dépôt chimique en phase vapeur, d'un dépôt chimique en phase vapeur assisté (p.ex. dépôt chimique en phase vapeur par laser, dépôt chimique en phase vapeur activé par de la lumière, dépôt chimique en phase vapeur par plasma, dépôt chimique en phase vapeur activé par des ions), d'une implantation d'ions, d'une épitaxie par jets moléculaires et d'un traitement thermique rapide, pour former des films d'antimoine ou des films contenant de l'antimoine.
PCT/US1998/024568 1997-11-24 1998-11-17 Produits d'addition d'antimoine/base de lewis utiles pour l'implantation d'ions sb et la formation de films d'antimoniure WO1999026955A1 (fr)

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AU21975/99A AU2197599A (en) 1997-11-24 1998-11-17 Antimony/lewis base adducts for sb-ion implantation and formation of antimonide films

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US08/977,507 US6005127A (en) 1997-11-24 1997-11-24 Antimony/Lewis base adducts for Sb-ion implantation and formation of antimonide films
US977,507 1997-11-24

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US6005127A (en) 1999-12-21
AU2197599A (en) 1999-06-15

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